Model studies on reactions occurring in oxidations of lignin with molecular oxygen in Alkaline Media

Basic reactions governing the degradation of lignin in oxidation with molecular oxygen are discussed emphasizing the radical (homolytic) or one-electron transfer-oxidations in the initial phase. The critical oxidation potentials (COP) according to Fieser were found to represent a useful measure for the ease of electron release from lignin-related phenolic models. At low alkalinity rough correlations were observed between the measured COPs and the initial oxygenation rates. The results obtained from quantum mechanical calculations of critical oxidation potentials are briefly discussed.The importance of phenoxy radicals and the hypothetical cyclohexadienone hydroperoxides as intermediates is outlined in view of such degradation reactions as oxidative side-chain eliminations, demethoxylations, and splitting of aromatic rings.Research performed at the Institute of Organic Chemistry, University of Vienna.